4-amino-2-quinolinone derivatives

ABSTRACT

The present invention relates to novel 4-amino-2-quinolinone derivatives of the formula (I) useful in agriculture, especially as fungicides, insecticides and herbicides ##STR1## wherein, R 1 , R 2 , R 3  and R 4  are independently hydrogen, halogen, C 1  -C 10  alkyl, C 1  -C 3  haloalkyl, C 1  -C 8  alkoxy, C 1  -C 3  haloalkoxy, C 1  -C 3  alkylthio, C 1  -C 3  haloalkyithio, NO 2 , CN, C 1  -C 4  alkoxy carbonyl, phenyl, phenoxy, benzoyl, benzenesulfonyl, benzyl or morpholine; R 5  is hydrogen, C 1  -C 6  alkyl, cyclopropyl, phenyl, halophenyl, benzyl or phenylthiomethyl; R 6  is hydrogen, C 1  -C 5  alkyl, C 3  -C 6  alkenyl or C 3  -C 6  alkynyl; and R 7  is ##STR2## wherein, R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , X, Y, m, n, p and q are defined within the description.

This is the U.S. national stage application of PCT/KR94/00079 filed Jun. 21, 1994, published as WO/95/00488 on Jan. 5, 1995.

BACKGROUND OF THE INVENTION

Field of the Invention

The present invention relates to novel 4-amino-2-quinolinone derivatives of the following formula (I) useful as fungicides, insecticides and herbicides. ##STR3## wherein, R₁, R₂, R₃ and R₄ are independently hydrogen, halogen, C₁ -C₁₀ alkyl, C₁ -C₃ haloalkyl, C₁ -C₈ alkoxy, C₁ -C₃ haloalkoxy, C₁ -C₃ alkylthio, C₁ -C₃ haloalkylthio, NO₂, CN, C₁ -C₄ alkoxy carbonyl, phenyl, phenoxy, benzoyl, benzenesulfonyl, benzyl or morpholine;

R₅ is C₁ -C₆ alkyl, cyclopropyl, phenyl, halophenyl, benzyl or phenylthiomethyl;

R₆ is selected from hydrogen, C₁ -C₅ alkyl, C₃ -C₆ alkenyl and C₃ -C₆ alkynyl group;

R₇ is ##STR4## wherein, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆ is hydrogen, halogen, C₁ -C₆ alkyl, alkoxyalkyl, halophenyl, phenyl or (R₂₀)₃ Si and R₈, R₉, R₁₀ are not hydrogen at the same time;

R₁₇ is hydrogen or C₁ -C₅ alkyl;

R₁₈, R₁₉ is C₁ -C₅ alkyl;

X is oxygen or sulfur;

Y is sulfur or --S(═O)--;

R₂₀ is C₁ -C₅ alkyl;

m, n, p, q is 0 to 4.

Description of the Related Art

Prior to this invention, one report on the synthesis of 3-acetyl-4-dimethylamino-2-quinolinone from phenylisocynate and 1-dimethylamino-3-oxo-1-butylene by 4+2! cycloaddition reaction (Helv. Chim. Acta., 1969, 52, 2641.) was disclosed but no attempt for the evaluation of biological activity of the related compounds was reported.

According to the known methods, it is difficult to introduce various substituents to aromatic ring, 4-amino group, and 3-acyl group of 2-quinolinone skeleton.

Especially, synthesis of 4-monosubstituted amino-2-quinolinones which are core of the present invention is impossible to be produced by known methods.

In the present invention, variety of new 4-amino-2-quinolinone derivatives having various substituents were synthesized conveniently from various amines and 4-sulfinyl-2-quinolinones of which synthesis was previously disclosed by present inventors (Korea Patent No.70672).

Moreover new 4-amino-2-quinolinone derivatives of the present invention showed powerful fungicidal activity as well as insecticidal and herbicidal activity.

Therefore, the present invention contains development of novel 4-amino-2-quinolinone derivatives that have superior fungicide, insecticide and herbicide activities and their preparation for use.

SUMMARY OF THE INVENTION

The objective of the present invention is to provide novel 4-amino-2-quinolinone derivatives of formula (I) which have fungicidal, insecticidal and herbicidal activity and their preparation processes.

Another objective is to provide agricultural preparation containing a compound of formula (I) as active ingredient.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to 4-amino-2-quinolinone compounds of the formula (I) and agricultural preparations containing compounds of the formula (I) as active ingredient. ##STR5## wherein, R₁, R₂, R₃, R₄, R₅, R₆ and R₇ are respectively defined as described previously.

In this invention, 4-amino-2-quinolinone compounds of the formula (I) were prepared by reacting 4-sulfinyl-2-quinolinone of formula (II) with the amines (HNR₆ R₇) of the formula (III) in presence of inert solvent. ##STR6## wherein, R₁, R₂, R₃, R₄, R₅, R₆ and R₇ are defined as previously and R₂₁ is C₁ -C₃ alkyl.

When the amine compound of formula (III) is in salt form, such as primary or secondary ammonium hydrochlorides (HNR₆ R₇ --HCl), sulfates, carbonates, oxalates or tosylates, 1˜2 equivalents of an acid remover, for example, trialkylamines (such as triethylamine) or inorganic base (such as sodium hydroxide, potassium carbonate), may be used.

The inert solvents used in the present invention may be, for example, ethers such as diethylether, diisopropyl ether, tetrahydrofuran, dioxane, diphenylether, etc.; hydrocarbons such as benzene, toluene, xylene, ligroine, etc.; hydrocarbon halides such as dichloroethane, chloroform, carbon tetrachloride, etc.; esters such as ethyl acetate, ethyl propionate, etc.; chlorobenzenes such as monochlorobenzene, dichlorobenzene, etc.; aprotic polar solvents such as N,N-dimethylformamide, dimethyl sulfoxide, etc. The above reaction can be carried out in the absence of solvent but for effective reaction use of proper solvent is recommended and pyridine and trialkylamine may be used for two purposes of base or a solvent.

The reaction can be carried out at 0°˜260° C., preferably between room temperature and boiling point of the solvent, and then the reaction time is preferably of 0.5˜8 hr.

As a result of the reaction, when the free amine compound (HNR₆ R₇) of formula (III) is used, the crude product is obtained by evaporating the solvent under the reduced pressure.

But, when the salt form of amine compound of formula (III) is used, the crude product may be obtained by following process; the solvent is evaporated under the reduced pressure; water is added to dissolve the salts; the resulting mixture is extracted with water-immiscible organic solvents such as methylenechloride, chloroform, ethyl acetate, etc.; and the organic layer is evaporated under the reduced pressure to afford the crude product.

Compounds (Ib) shown below can be obtained by acid hydrolysis of compounds (Ia), a kind of 4-amino-2-quinolinone derivatives of formula (I) ##STR7## wherein, R₁, R₂, R₃, R₄, R₅, R₆ and R₁₈ are defined as previously.

The hydrolysis reaction of compounds (Ia) to compounds (Ib) can be done in the presence of mineral acids such as hydrochloric acid, sulfuric acid, etc. or organic acids such as acetic acid, propionic acid, etc. and the reaction could be carried from room temperature to the boiling point of the solvent.

The 4-amino-2-quinolinone derivatives of formula (I) described above may be purified by column chromatography or recrystallized from the following solvents; alcohol solvents such as methanol, ethanol, etc.; esters of organic acid such as ethyl acetate, methyl acetate, etc.; hydrocarbon solvents such as pentane, hexane, etc.; ethers such as ethylether, tetrahydrofuran, etc.

New compounds of 4-amino-2-quinolinone (I) prepared by present invention are typically listed in following Table (I).

                                      TABLE 1                                      __________________________________________________________________________     4-Amino-2-quinolinone derivatives                                               ##STR8##                                      (I)                             No.                                                                               R.sub.1                                                                             R.sub.2                                                                             R.sub.3                                                                             R.sub.4                                                                           R.sub.5                                                                             R.sub.6                                                                               R.sub.7     m.p. (°C.)                 __________________________________________________________________________     1  CF.sub.3                                                                            H    H    H  Me                                                                                   ##STR9##                                                                              ##STR10##  36-38                             2  Cl   Cl   H    H  Me                                                                                   ##STR11##                                                                             ##STR12##  48-50                             3  Cl   H    H    CF.sub.3                                                                          Me                                                                                   ##STR13##                                                                             ##STR14##  75-77                             4  Me   F    H    H  Me                                                                                   ##STR15##                                                                             ##STR16##  61-64                             5  CN   H    H    H  Me                                                                                   ##STR17##                                                                             ##STR18##  70-71                             6  Cl   H    H    Cl Me                                                                                   ##STR19##                                                                             ##STR20##  76-78                             7  CF.sub.3                                                                            H    Cl   H  c-Pr                                                                                 ##STR21##                                                                             ##STR22##  104-107                           8  CF.sub.3                                                                            H    Cl   H  i-Pr                                                                                 ##STR23##                                                                             ##STR24##  83-85                             9  CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR25##  191-193                           10 CF.sub.3                                                                            H    Cl   H  i-Pr H                                                                                      ##STR26##  159-161                           11 CF.sub.3                                                                            H    Cl   H  Et   H                                                                                      ##STR27##  171-172                           12 CF.sub.3                                                                            H    Cl   H  Me   Me                                                                                     ##STR28##  86-87                             13 CF.sub.3                                                                            H    Cl   H  i-Pr Me                                                                                     ##STR29##  99-101                            14 CF.sub.3                                                                            H    Cl   H  c-Pr Me                                                                                     ##STR30##  118-120                           15 CF.sub.3                                                                            H    H    H  Me   Me                                                                                     ##STR31##  64-69                             16 CF.sub.3                                                                            H    Cl   H  Et   Me                                                                                     ##STR32##  70-72                             17 Cl   Cl   H    H  Me   Me                                                                                     ##STR33##  110-112                           18 Cl   Cl   H    H  Me   H                                                                                      ##STR34##  210-211                           19 CF.sub.3                                                                            F    H    H  Me   H                                                                                      ##STR35##  161-162                           20 Cl   H    H    NO.sub.2                                                                          Me   H                                                                                      ##STR36##  213-214                           21 CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR37##  179-181                           22 CF.sub.3                                                                            H    Cl   H  Et   H                                                                                      ##STR38##  185-186                           23 H    H    n-C.sub.6 H.sub.13                                                                  H  Me   H                                                                                      ##STR39##  129-132                           24 CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR40##  210-212                           25 Me   H    H    H  Me   H                                                                                      ##STR41##  232-234                           26 Cl   H    H    NO.sub.2                                                                          H    H                                                                                      ##STR42##  217-219                           27 Cl   Cl   H    H  Me   H                                                                                      ##STR43##  245-249                           28 CF.sub.3                                                                            H    Cl   H  i-Pr H                                                                                      ##STR44##  166-168                           29 CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR45##  213-215                           30 CF.sub.3                                                                            H    Cl   H  i-Pr H                                                                                      ##STR46##  167-169                           31 CF.sub.3                                                                            H    Cl   H  i-Pr H                                                                                      ##STR47##  55-56                             32 CF.sub.3                                                                            H    Cl   H  i-Pr H                                                                                      ##STR48##  53-54                             33 CF.sub.3                                                                            H    Cl   H  i-Pr H                                                                                      ##STR49##  E & Z                             34 CF.sub.3                                                                            H    Cl   H  i-Pr H                                                                                      ##STR50##  177-178                           35 CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR51##  183-184                           36 CF.sub.3                                                                            H    Cl   H  Me   H      H.sub.2 CCN 218-220                           37 CF.sub.3                                                                            H    Cl   H  i-Pr H                                                                                      ##STR52##  129-130                           38 CF.sub.3                                                                            H    Cl   H  i-Pr H                                                                                      ##STR53##  114-116                           39 CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR54##  168-169                           40 CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR55##  191-193                           41 CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR56##  181-182                           42 CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR57##  172-173                           43 CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR58##  191-192                           44 CF   H    Cl   H  Et   H                                                                                      ##STR59##  183-184                           45 CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR60##  104-105                           46 CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR61##  132-133                           47 CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR62##  240-241                           48 CF.sub.3                                                                            H    Cl   H  i-Pr H                                                                                      ##STR63##  185-186                           49 CF.sub.3                                                                            H    Cl   H  Et   H                                                                                      ##STR64##  154-155                           50 CF.sub.3                                                                            H    Cl   H  Et   H                                                                                      ##STR65##  153-154                           51 CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR66##  172-173                           52 CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR67##  156-157                           53 CF.sub.3                                                                            H    Cl   H  Et   H                                                                                      ##STR68##  183-184                           54 CF.sub.3                                                                            H    Cl   H  Et   H                                                                                      ##STR69##  124-126                           55 CF.sub.3                                                                            H    Cl   H  Et   H                                                                                      ##STR70##  188-189                           56 CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR71##  196-197                           57 CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR72##  134-135                           58 CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR73##  181-182                           59 CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR74##  111-112                           60 CF.sub.3                                                                            H    Cl   H  Et   H                                                                                      ##STR75##  181-182                           61 CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR76##  152-153                           62 CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR77##  170-172                           63 CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR78##  185-186                           64 CF.sub.3                                                                            H    Cl   H  Et   H                                                                                      ##STR79##  87-88                             65 CF.sub.3                                                                            H    Cl   H  Et   H                                                                                      ##STR80##  91-94                             66 CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR81##  127-130                           67 CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR82##  E & Z                             68 CF.sub.3                                                                            H    Cl   H  Et   H                                                                                      ##STR83##  E & Z                             69 CHCHCHCH  Cl   H  c-Pr H                                                                                      ##STR84## 222 (dec.)                         70 CF.sub.3                                                                            H    H    H  Me   H                                                                                      ##STR85## 192-194                            71 Cl   H    H    H  Et   H                                                                                      ##STR86## 212-214                            72 CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR87## 136-137                            73 CF.sub.3                                                                            H    Cl   H  c-Pr                                                                                 ##STR88##                                                                             ##STR89## 140-142                            74 CF.sub.3                                                                            H    Cl   H  i-Bu H                                                                                      ##STR90## 179-180                            75 CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR91## 136-137                            76 CF.sub.3                                                                            H    Cl   H  Et   H                                                                                      ##STR92## 149-150                            77 CF.sub.3                                                                            H    Cl   H  i-Pr H                                                                                      ##STR93## 135-136                            78 CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR94## E & Z                              79 H    H    Cl   H  Me   H                                                                                      ##STR95## 166-168                            80 F    H    H    H  H    H                                                                                      ##STR96## 206-208                            81 Me   H    H    H  Me   H                                                                                      ##STR97## 229-231                            82 CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR98## 227-228                            83 CF.sub.3                                                                            H    Cl   H  Et   H                                                                                      ##STR99## 191-193                            84 CF.sub.3                                                                            H    Cl   H  i-Pr H                                                                                      ##STR100##                                                                               166-167                            85 CF.sub.3                                                                            H    Cl   H  Et                                                                                   ##STR101##                                                                            ##STR102##                                                                               91-94                              86 CF.sub.3                                                                            H    Cl   H  Me                                                                                   ##STR103##                                                                            ##STR104##                                                                               115-117                            87 CF.sub.3                                                                            H    Cl   H  i-Pr H                                                                                      ##STR105##                                   88 H    OCH.sub.2 CH.sub.2 O                                                                     H  c-Pr H                                                                                      ##STR106##                                                                               230 (dec.)                         89 CF.sub.3                                                                            H    Cl   H  i-pr H                                                                                      ##STR107##                                                                               113-114                            90 CF.sub.3                                                                            H    Cl   H  i-Pr H                                                                                      ##STR108##                                                                               154-155                            91 CF.sub.3                                                                            H    Cl   H  i-Pr H                                                                                      ##STR109##                                                                               196-197                            92 CF.sub.3                                                                            H    Cl   H  i-Bu H                                                                                      ##STR110##                                                                               128-130                            93 CF.sub.3                                                                            H    Cl   H  i-Pr                                                                                 ##STR111##                                                                            ##STR112##                                                                               93-94                              94 CF.sub.3                                                                            H    H    H  Me                                                                                   ##STR113##                                                                            ##STR114##                                                                               94-95                              95 CF.sub.3                                                                            H    Cl   H  Et   H                                                                                      ##STR115##                                                                               159-161                            96 CF.sub.3                                                                            H    Cl   H  i-Bu H                                                                                      ##STR116##                                                                               174-175                            97 CF.sub.3                                                                            H    Cl   H  i-Pr H                                                                                      ##STR117##                                                                               140-142                            98 CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR118##                                                                               166-168                            99 CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR119##                                                                               200-201                            100                                                                               CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR120##                                   101                                                                               CF.sub.3                                                                            H    Cl   H  PhCH.sub.2                                                                          H                                                                                      ##STR121##                                                                               154-156                            102                                                                               CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR122##                                                                               146-147                            103                                                                               CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR123##                                                                               125-127                            104                                                                               CF.sub.3                                                                            H    Cl   H  i-Bu H                                                                                      ##STR124##                                                                               100-102                            105                                                                               CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR125##                                                                               122-126                            106                                                                               CF.sub.3                                                                            H    Cl   H  Et   H                                                                                      ##STR126##                                                                               107-109                            107                                                                               CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR127##                                                                               185-186                            108                                                                               CF.sub.3                                                                            H    Cl   H  i-Bu H                                                                                      ##STR128##                                                                               121-123                            109                                                                               CF.sub.3                                                                            H    Cl   H  Et   H                                                                                      ##STR129##                                                                               164-166                            110                                                                               CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR130##                                                                               233-235                            111                                                                               CF.sub.3                                                                            H    Cl   H  i-Pr H                                                                                      ##STR131##                                                                               222-224                            112                                                                               Cl   H    H    H  Et   H                                                                                      ##STR132##                                                                               238-239                            113                                                                               CF.sub.3                                                                            H    Cl   H  Et   H                                                                                      ##STR133##                                                                               141-143                            114                                                                               CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR134##                                                                               147-149                            115                                                                               CF.sub.3                                                                            H    Cl   H  i-Pr H                                                                                      ##STR135##                                                                               100-102                            116                                                                               CF.sub.3                                                                            H    Cl   H  i-Pr H                                                                                      ##STR136##                                                                               144-145                            117                                                                               CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR137##                                                                               167-168                            118                                                                               CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR138##                                                                               107-110                            119                                                                               CF.sub.3                                                                            H    Cl   H  Et   H                                                                                      ##STR139##                                                                               103-105                            120                                                                               CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR140##                                                                               135-137                            121                                                                               CF.sub.3                                                                            H    Cl   H  i-Bu H                                                                                      ##STR141##                                                                               92-94                              122                                                                               H    H    F    H  Me   H                                                                                      ##STR142##                                                                               307-309                            123                                                                               CF.sub.3                                                                            H    Cl   H  Et   H                                                                                      ##STR143##                                                                               243-244                            124                                                                               CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR144##                                                                               152-153                            125                                                                               CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR145##                                                                               135-136                            126                                                                               CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR146##                                                                               109-111                            127                                                                               CF.sub.3                                                                            H    Cl   H  Et   H                                                                                      ##STR147##                                                                               117-118                            128                                                                               CF.sub.3                                                                            H    Cl   H  c-Pr H                                                                                      ##STR148##                                                                               139-141                            129                                                                               CF.sub.3                                                                            H    Cl   H  i-Bu H                                                                                      ##STR149##                                                                               94-95                              130                                                                               CF.sub.3                                                                            H    Cl   H  Me   H                                                                                      ##STR150##                                                                               232-234                            131                                                                               CF.sub.3                                                                            H    Cl   H  i-Bu H                                                                                      ##STR151##                                                                               179-181                            __________________________________________________________________________

Preparation of the present compounds of formula (I) is illustrated further in the following examples.

EXAMPLE 1 6-Chloro-3-cyclopropanecarbonyl-4-(2,2-dimethoxyethylamino)-8-trifluoromethyl-2-quinolinone (9)

6-Chloro-3-cyclopropanecarbonyl-4-methylsulfoxy-8-trifluormethyl-2-quinolinone (377 mg, 1 mmol) and 2,2-dimethoxyethylamine (105 mg, 1 mmol) were dissolved in tetrahydrofurane (20 ml) and stirred for 24 hr at room temperature. After completion of reaction, solvent was removed under reduced pressure and residue was recrystallized from ethanol to give desired product (335 mg, yield: 80%).

¹ H-NMR (CDCl₃): δ0.7-1.2(m,4H), 3.4(s, 6H), 3.6-3.8(m,1H), 4.4(t, 1H), 4.5-4.9(m, 2H), 7.7(d, 1H), 8.8 (d, 1H), 9.5(br, 1H), 11.6(br, 1H).

EXAMPLE 2 6-Chloro-4-(2,2-dimethoxyethylamino)-3-isobutyryl-8-trifluoromethyl-2-quinolinone (10)

6-Chloro-3-isobutyryl-4-methylsulfoxy-8-trifluoromethyl-2-quinolinone (379 mg, 1 mmol) and 2,2-dimethoxyethylamine (105 mg, 1 mmol) were used and the reaction was carried out as in the above process of example 1 to obtain the desired product (307 mg, yield: 73%).

¹ H NMR (CDCl₃): δ 1.5(d, 6H), 3.6-3.8(m, 1H), 3.8(s, 6H), 4.4(t, 1H), 4.5-4.9(m, 2H), 8.1(d, 1H), 8.8(d, 1H), 9.9(br, 1H), 12.2(br, 1H).

EXAMPLE 3 3-Acetyl-6-chloro-4-(N-methyl-N'-propargylamino)-8-trifluoromethyl-2-quinolinone (12)

3-Acetyl-6-chloro-4-methylsulfoxy-8-trifluoromethyl-2-quinolinone (351 mg, 1 mmol) and N-methyl-N'-propargylamine (69 mg, 1 mmol) were used and the reaction was carried out as in the above process of example 1 to obtain the desired product (235 mg, yield: 66%).

¹ H NMR (CDCl₃): δ2.6(t, 1H), 3.0(s, 3H), 3.4(s, 3H), 4.6 (d, 2H), 8.2 (d, 1H),

8.6 (d, 1H), 14.0 (br, 1H).

EXAMPLE 4 3-Acetyl-4-(N-methyl-N'-propargylamino)-8-trifluoromethyl-2-quinolinone (15)

3-Acetyl-4-methylsulfoxy-8-trifluoromethyl-2-quinolinone (317 mg, 1 mmol) and N-methyl-N'-propargylamine (69 mg, 1 mmol) were used and the reaction was carried out as in the above process of example 1 to obtain the desired product (210 mg, yield: 65%).

¹ H NMR (CDCl₃): δ 2.5 (t, 1H), 2.9 (s, 3H), 3.3(s, 3H), 4.5(d, 2H), 7.4(t, 1H), 8.2(d, 1H), 8.5(d, 1H), 9.6(br, 1H).

EXAMPLE 5 6-Chloro-3-cyclopropanecarbonyl-4-propargylamino-8-trifluormethyl-2-quinolinone (21)

6-Chloro-3-cyclopropanecarbonyl-4-methylsulfoxy-8-trifluormethyl-2-quinolinone (377 mg, 1 mmol) and propargylamine (55 mg, 1 mmol) were used and the reaction was carried out as in the above process of example 1 to obtain the desired product (265 mg, yield: 72%).

¹ H NMR (CDCl₃): δ 1.3-1.6(m, 4H), 2.9(t, 1H), 3.9-4.3(m, 1H), 4.6(q, 2H), 8.2(d, 1H), 8.8(d, 2H), 12.4(br, 1H).

EXAMPLE 6 3-Acetyl-6-chloro-4-propargylamino-8-trifluoromethyl-2-quinolinone (24)

3-Acetyl-6-chloro-4-methylsulfoxy-8-trifluoromethyl-2-quinolinone (351 mg, 1 mmol) and propargylamine (55 mg, 1 mmol) were used and the reaction was carried out as in the above process of example 1 to obtain the desired product (284 mg, yield: 83%).

¹ H NMR (CDCl₃): δ 2.9(t, 1H), 3.0(s, 3H), 4.5(q, 2H), 8.0(d, 1H), 8.8(d, 2H), 12.3(br, 1H).

EXAMPLE 7 6-Chloro-4-(3,3-diethoxypropylamino)-3-isobutyryl-8-trifluoromethyl-2-quinolinone (31)

6-Chloro-3-isobutyryl-4-methylsulfoxy-8-trifluoromethyl-2-quinolinone (379 mg, 1 mmol) and 3,3-diethoxypropylamine (147 mg, 1 mmol) were used and the reaction was carried out as in the above process of example 1 to obtain the desired product (335 mg, yield: 78%).

¹ H NMR (CDCl₃): δ 0.7-1.5(m, 12H), 2.0-2.4(m, 2H),3.2-4.0 (m, 6H), 4.2 (m, 1H), 4.7 (t, 1H), 7.8(d, 1H), 8.0(br, 1H), 11.9(br, 1H).

EXAMPLE 8 6-Chloro-3-isoburyryl-4-(3-oxopropylamino)-8-trifluoromethyl-2-quinolinone (32)

6-Chloro-4-(3,3-diethoxypropylamino)-3-isobutyryl-8-trifluoromethyl-2-quinolinone (31) was dissolved in 80% aqueous acetic acid (20 ml) and stirred for 2 h at 70° C. After cooling to room temperature, water (20 ml) was added and the mixture was extracted with ethyl acetate (30 ml). Organic layer was dried (MgSO₄), filtered, evaporated and purified by silicagel chromatograph (n-Hexane and Ethyl acetate) to give desired product (280 mg, yield: 72%).

¹ H NMR (CDCl₃): δ 1.3(d, 6H), 3.1(t, 2H), 3.7(q, 2H), 4.2(m, 1H), 7.8(d, 1H), 8.5(d, 1H), 9.1(br, 1H), 10.0(s, 1H), 11.2(br, 1H).

EXAMPLE 9 3-Acetyl-6-chloro-8-trifluoromethyl-4-(3-trimethylsilyl-propargyl-amino)-2-quinolinone (42)

3-Acetyl-6-chloro-4-methylsulfoxy-8-trifluoromethyl-2-quinolinone (351 mg, 1 mmol), 3-trimethylsilylpropargylamine hydrochloride (164 mg, 1 mmol) and excess triethylamine in tetrahydrofurane (20 ml) were stirred for 24 h at room temperature. After evaporating the solvent, 20 ml of methylene chloride was added and the mixture was washed with water (20 ml). Drying (MgSO₄) and removing the solvent under reduced pressure gave crude product. Recrystallization in ethanol gave pure product (330 mg, yield: 80%).

¹ H NMR (CDCl₃): δ 0.2(s, 9H), 2.7(s,3H), 4.3(d,2H), 7.8(d, 1H), 8.5(br, 1H), 8.6(d, 1H), 12.0(br, 1H).

EXAMPLE 10 6-Chloro-4-propargylamino-3-propionyl-8-trifluoromethyl-2-quinolinone (44)

6-Chloro-4-methylsulfoxy-3-propionyl-8-trifluoromethyl-2-quinolinone (365 mg, 1 mmol) and propargylamine (55 mg, 1 mmol) were used and the reaction was carried out as in the above process of example 1 to obtain the desired product (310 mg, yield: 87%).

¹ H NMR (CDCl₃): δ 1.2(t, 3H), 2.7(t, 1H), 3.4(q, 2H), 4.3(d, 2H), 7.9(d, 1H), 8.6(br, 1H), 8.7(d, 1H), 12.2(br, 1H).

EXAMPLE 11 3-Acetyl-6-chloro-4-(1,1-dimethylpropargylamino)-8-trifluoromethyl-2-quinolinone (51)

3-Acetyl-6-chloro-4-methylsulfoxy-8-trifluoromethyl-2-quinolinone (351 mg, 1 mmol) and 1,1-dimethytpropargylamine (83 mg, 1 mmol) were used and the reaction was carried out as in the above process of example 1 to obtain the desired product (322 mg, yield: 87%).

¹ H NMR (CDCl₃): δ 1.5(s, 6H), 2.5(t, 1H), 2.6(s, 3H), 7.7(m, 1H), 8.4(m, 1H), 9.1(br, 1H), 12.0(br, 1H).

EXAMPLE 12 3-Acetyl-6-chloro-4-(3-phenylallylamino)-8-trifluoromethyl-2-quinolindne (62)

3-Acetyl-6-chloro-4-methylsulfoxy-8-trifluoromethyl-2-quinolinone (351 mg, 1 mmol) and 3-phenylallylamine (83 mg, 1 mmol) were used and the reaction was carried out as in the above process of example 1 to obtain the desired product (286 mg, yield: 68%).

¹ H NMR (CDCl₃): δ 2.8(s,3H), 4.3(t, 2H), 6.0-6.7(m, 2H), 7.4(s, 5H), 7.7(d, 1H), 8.1 (br, 1H), 8.5(d, 1H), 12.1(br, 1H).

EXAMPLE 13 6-Chloro-4-(2-chloroallylamino)-3-propionyl-8-trifluoromethyl-2-quinolinone (76)

6- Chloro-4-methylsulfoxy-3-propionyl-8-trifluoromethyl-2-quinolinone (365 mg, 1 mmol) and 2-chloroallylamine (92 mg, 1 mmol) were used and the reaction was carried out as in the above process of example 1 to obtain the desired product (279 mg, yield: 71%).

¹ H NMR (CDCl₃): δ 1.2(t, 3H), 3.3(q, 2H), 4.2(d, 2H), 5.6(s, 2H), 7.8(d, 1H), 8.0(br, 1H), 8.5(d, 1H), 12.3(br, 1H).

EXAMPLE 14 6-Chloro-4-(N,N'-dipropargylamino)-3-isobutyryl-8-trifluommethyl-2-quinolinone (93)

6-Chloro-3-isobutyryl-4-methylsulfoxy-8-trifluoromethyl-2-quinolinone (379 mg, 1 mmol) and N,N'-dipropargylamine (93 ml, 1 mmol) were used and the reaction was carried out as in the above process of example 1 to obtain the desired product (290 mg, yield: 71%).

¹ H NMR (CDCl₃): δ 1.2(d, 6H), 2.3(t, 2H), 4.0-4.3(m, 1H), 4.3(d, 4H), 8.0(d, 1H), 8.3(d, 1H), 13.1(br, 1H).

EXAMPLE 15 3-Acetyl-6-chloro-4-(3-phenylpropargylamino)-8-trifluoromethyl-2-quinolinone (99)

3-Acetyl-6-chloro-4-methylsulfoxy-8-trifluoromethyl-2-quinolinone (351 mg, 1 mmol) and 3-phenylpropargylamine hydrochloride (167 mg, 1 mmol) were used and the reaction was carried out as in the above process of example 10 to obtain the desired product (305 mg, yield: 73%).

¹ H NMR (CDCl₃): δ 2.7(s, 3H), 4.5(d, 2H), 7.5(s, 5H), 7.8(d, 1H), 8.6(d, 2H), 12.0(br, 1H).

EXAMPLE 16 3-Acetyl-6-chloro-4-methylthioethylamino-8-trifluoromethyl-2-quinolinone (102)

3-Acetyl-6-chloro-4-methylsulfoxy-8-trifluoromethyl-2-quinolinone (351 mg, 1 mmol) and methylthioethylamine (91 mg, 1 mmol) were used and the reaction was carried out as in the above process of example 1 to obtain the desired product (287 mg, yield: 76%).

¹ H NMR (CDCl₃): δ 2.15(s, 3H), 2.7(s, 3H), 2.8(t, 2H), 3.6(q, 2H), 7.7(br, 1H), 8.1(br, 1H), 8.5(br, 1H), 12.0(br, 1H).

EXAMPLE 17 3-Acetyl-6-chloro-4- 2-(4-fluorophenyl)-2,3-butadienylamino!-8-trifluoromethyl-2-quinolinone (114)

3-Acetyl-6-chloro-4-methylsulfoxy-8-trifluoromethyl-2-quinolinone (351 mg, 1 mmol) and methylthioethylamine (91 mg, 1 mmol) were used and the reaction was carried out as in the above process of example 1 to obtain the desired product (369 mg, yield: 82%).

¹ H NMR (CDCl₃): δ 2.6(s, 3H), 3.6(t,2H), 5.2(t, 2H), 7.2(m, 4H), 7.8(d, 1H), 8.5(br, 1H), 8.6(d, 1H), 11.8(br, 1H).

The compounds of formula (I) according to the present invention have highly curative and protective fungicidal activity for plant phathogens as follows; for example, rice blast (Piricularia oryzae), rice sheath blight (Rhizoctonia solani), cucumber gray mold (Botrytis cinerea), cucumber powdery mildew (Sphaerotheca fuliginea), cucumber downy mildew (Pseudoperonospora cubensis), grape downy mildew (Plasmopora viticola), tomato late blight (Phytophthora infestans), rice brown spot (Cochliobolus miyabeanus), peanut brown leaf spot (Cercospora arachidicola), barley powdery mildew (Erysiphe graminis), wheat leaf rust (Puccinia recondita), wheat stem rust (Puccinis graminis), and wheat eye spot (Pseudocercosporella herpotrichoides). Especially, the compounds of present invention showed strong fungicidal activity against rice blast and wheat leaf rust.

The fungicidal activities of 4-amino-2-quinolinone derivatives of formula (I) according to the present invention prepared by the above examples were tested as follow; wherein all the test chemicals were readily dispersed in a standard formulation of acetone in water and a surfactant. Ten ml of acetone containing 10 mg of the chemical was diluted in 90 ml of Tween-20 solution producing 100 ppm solution of chemicals of above examples. Fifty ml of this chemical solution was sprayed to plants on the turntable at the same time. Two pots of plants were duplicately tested for fungicidal activity against 6 plant diseases, respectively.

TEST 1

Fungicidal test for rice blast (RCB)

Evaluation of activity against blast was done with rice plants in the second leaf stage, grown in 5 cm pots with a foliage spray. Fifty ml test material was sprayed on the foliage. After the spray deposit had dried, the plants were inoculated with a suspension of conidia in water (1×10⁶ spores/ml) and placed in a dew chamber at 25° C. for 24 hrs. For inocuhm preparation, rice blast fungus was incubated on rice polish agar medium at 26° C. for 2 weeks, and then scratched airial roycelia with rubber and irradiated with near UV light for 2 days. The plants were then held in lighted growth chamber (26±2° C., 85%) for an additional 5 days, and rated on the disease severity.

TEST 2

Fungicidal test for rice sheath blast (RSB)

Rice plants in the third leaf stage were sprayed with 50 ml of chemical solution on the turntable. One day after drying, treated plants were inoculated by injecting inoculum, incubated in wheat bran medium at 25° C. for 7 days, macerated into the mixer at the base of the rice plants. The pots were moved to a lighted dew chamber at 28° C. and then held for 5 days. The disease severity of each pot was examined and compared with the standard rating diagram.

TEST 3

Fungicidal test for cucumber gray mold (CGM)

Cucumber plants grown in the first leaf stage were sprayed with 50 ml of chemical solution while pots were rotated on the truntable. After the spray deposit had dried for one day, the treated foliage of cucumber was inoculated with conidia (1×10⁶ spores/ml of B. cinerea), incubated on potato dextrose agar medium at 25° C. for 15 days by leaf spray to all four sides of plants until just before runoff and then placed in 20° C. dew chamber for 4-5 days. The disease rating was made by examining the treated plants and comparing the percent disease on a leaf with the standard rating diagram.

TEST 4

Fungicidal test for tomato late blight (TLB)

Tests were carried out onto tomato plants grown in 5 cm polyvinyl pots for 14 days by leaf spray. The foliage was sprayed to run off with the test chemical while the plant rotated on a turntable. After the spray deposit dried for one day, the treated plants were inoculated by spraying them with a suspension of zoosporangia (1×10⁵ zoosporangia/ml) incubated on V-8 juice agar medium at 20° C. for 2 weeks and then placed in a dew chamber at 18° C. for 48 hrs. The disease severity was rated after 4 days of inoculation.

TEST 5

Fungicidal test for wheat leaf rust (WLR)

Tests were carried out on wheats (cultivar; Chokwang) grown in polyvinyI pots (diameter; 5 cm) for 7 days by foliage spray. The first leaf was sprayed while plants were rotating on a turntable with 50 ml of a chemical solution. After the spray deposit dried, plants were dusted with a uredospores colonled on the second leaf of wheat and placed in a moist chamber at 20° C. for 24 hours. One day after inoculation, plant were moved to the plant growth chamber (20° C., 70% RH) for inducing the disease. The fungicidal effect of the applied chemicals was investigated by observing the share of diseased area after ten days.

TEST 6

Fungicidal test for barley powdery mildew (BPM)

The barley powdery mildew is an obligately parasitic fungus that must be transferred directly from infected plants to healthy plants in a relatively dry environment. The host plants (cultivar; Allbori) sowed in polyvinyl pot (diameter; 5 cm) were grown in a greenhouse for 7 days. Healthy young barley with fully expanded primary leaf was sprayed with a suspension of a test material. One day after drying, the applied plants were dusted with conidia of Erysiphe graminis formed on the primary leaf of barley. The inoculated plants were placed in a plant growth chamber at 22°˜24° C. and then induced with the powdery mildew. The disease severity was rated after 7 days of inoculation.

Fungicidal activity of test chemicals against the above 6 plant diseases is shown in Table 2 calculated by formula below. ##EQU1##

                  TABLE 2                                                          ______________________________________                                         Fungicidal activity of the 4-amino-2-quinolinone of formula (I)                Comp. No.                                                                               RCB     RSB     CGM   TLB   WLR   BPM                                 ______________________________________                                         2        96      25      50    34    99    63                                  7        21      40      0     26    98    58                                  8        86      45      50    30    95    26                                  12       99      65      0     10    100   95                                  13       100     5       8     0     98    76                                  14       100     0       25    0     99    71                                  16       94      40      60    0     100   100                                 17       99      20      44    20    99    92                                  21       97      60      0     0     99    0                                   22       90      85      44    20    99    0                                   24       99      45      0     29    99    0                                   28       99      20      0     32    100   73                                  29       99      100     0     0     100   0                                   30       88      53      0     20    95    0                                   31       91      5       44    25    100   60                                  32       25      11      19    53    100   10                                  33       50      95      38    0     100   25                                  35       99      35      8     13    98    0                                   38       0       53      0     8     100   76                                  44       100     82      15    46    100   0                                   45       99      18      0     53    95    0                                   46       100     65      0     49    100   71                                  53       99      20      0     69    98    14                                  54       0       67      0     56    99    25                                  57       99      60      0     79    95    9                                   59       96      47      0     83    98    30                                  64       99      40      0     87    100   0                                   65       57      0       0     72    95    30                                  67       99      47      0     95    100   0                                   68       89      0       0     36    100   30                                  70       99      0       15    52    53    0                                   72       99      78      0     13    98    0                                   74       99      0       28    78    96    9                                   75       99      94      46    74    99    55                                  76       100     56      34    74    99    0                                   77       99      44      28    83    100   0                                   78       99      78      4     33    99    9                                   85       100     6       0     83    99    77                                  86       99      17      0     74    99    38                                  87       99      40      0     55    99    0                                   92       99      25      20    21    100   31                                  93       95      0       15    7     99    88                                  94       100     50      8     29    93    88                                  ______________________________________                                    

As shown in the Table 2, the compounds of present invention of formula (I) have broad and high fungicidal activity against tested plant diseases, especially, rice blast and wheat leaf rust.

Also, the compounds according to the present invention have high insecticidal and miticidal activity against noxious insects, for example, house fly, mosquito, cockroach and agricultral insects, for example, Hemiptera such as small brown plant hopper (Laodephax striatellus Fallen), brown plant hopper (Nilaparvata lugens Stail), white-backed rice plant hopper (Sogatella furcifera Horvath), green rice leaf hopper (Nephotettix cincticeps Uhler), greenhouse whitefly (Trialeurodes vaporariorum Westwood), and green peach aphid (Myzus persicae Sulzer); Lepidoptera such as apple leafminer (Phyllonorycter ringoniella Matsumura), diamond-back moth (Plutella xylostella Curtis), rice armyworm (Pseuclaletia separata Walker), cabbage to armyworm (Mamestra brassicae Linnaeus), tobacco cutworm (Spodoptera litura Fablicius), and common cabbage worm (Pieris rapae Linnaeus); Coleoptera such as rice leaf beetle (Oulema oryzae Kuiwayama), and rice-plant weevil rice curculio (Echinocnemus squameus Billbery).

The insecticidal activity of the compounds of the formula (I) according to the present invention was tested by Tests 7˜10 as shown below.

The Primary Screening (PRI) was designed to detect initial pest control activity of experimental compounds. The types of activity assayed were acute toxicity and growth disruption. The bioassays were designed to detect contact and ingestion activity.

The stages rested were as follows: adult brown planthopper (BPH), green peach aphid (GPA), and two-spotted spider mire (TSSM), and 3rd instar diamond-back moth (DBM). All experimental compounds were formulated in 5 ml of acetone containing 25 mg of 4-amino-2-quinolinone derivatives of formular (I) and diluted with 45 ml Triton X-100 (100 ppm) solution producing 500 ppm solution of chemicals of present invention.

Formulated compounds were applied to the test species with the individual application methods, respectively.

TEST 7

Insecticidal test for brown plant hopper (BPH)

Root parts of six rice seedlings (cultivar: Dongjin; 5-6 cm in length; 5-10 day old) were rolled with cotton wool pads and rice seedlings were put into the glass test tubes (Φ 3×15 cm) containing 2 ml water. Three to five day-old adult BPH (20 individuals) were collected from rearing cages by an aspirator, and placed into test tubes.

Test chemicals were dissolved in 5 ml acetone (100%), formulated to the proper concentration in Triton X-100 (100 ppm), and then sprayed onto the BPH directly. The test tubes were covered with nylon cloth and held in an incubator at 25° C. Insect mortalities were recorded at 24 and 48 hours after treatment.

TEST 8

Insecticidal test for green peach aphid (GPA)

Excised tobacco leaf disks (5.5 cm in diameter) were dipped into the prepaxed test chemical solutions (30 sec) and taken out. After drying (30 min), leaf disks were placed in the petridishes (Φ 5.5×2 cm) and apterous female adult GPAs (20 individuals) were introduced. All petridishes were covered and held in an incubator at 25° C. Insect mortalities were recorded at 24 and 48 hours after treatment.

TEST 9

Insecticidal test for two-spotted spider mite (TSSM)

Excised kidney bean leaf disks (2.5 cm in diameter) were placed on water saturated cotton wool pads fitted into petridishes (Φ5.5×2 cm). Female adult TSSMs (30 individuals) were placed on leaf disks and prepared test chemicals were sprayed. The petridishes were covered and held in an incubator at 25° C. Mite mortalities were recorded at 24 and 48 hours after treatment.

TEST 10

Insecticidal test for diamond-back moth (DBM)

Test chemicals were dissolved in 5ml acetone (100%) and formulated to the proper concentration in Triton X-100 (100 ppm). Excised cabbage leaf disks (5 cm in diameter) were dipped into the solution (30 sec) and taken out. After drying (30 min.), leaf disks were placed in the petridishes (Φ 5×1 cm) and 3rd instar DBM larvae (10 individuals) were introduced. All petridishes were covered and held in an incubator at 25° C. Insect mortalities were recorded at 24 and 48 hours after treatment.

The mortality (%) of test chemical against the above insects was calculated by the below formula to list the result as the following Table 3. ##EQU2##

                  TABLE 3                                                          ______________________________________                                         Insecticidal effects for 4-amino-2-quinolinone of the formula (I)              Comp. No.    BPH    GPA        DBM  TSSM                                       ______________________________________                                         2            0      0          0    100                                        10           10     0          100  0                                          12           0      0          90   100                                        13           0      0          100  100                                        16           0      0          80   100                                        21           0      0          100  0                                          22           0      0          100  0                                          24           0      0          100  0                                          28           0      0          100  0                                          30           0      0          100  0                                          35           0      0          100  0                                          37           0      0          100  0                                          38           0      0          100  73                                         39           0      0          100  0                                          41           0      0          100  0                                          44           0      0          100  0                                          46           0      0          100  0                                          49           0      0          100  0                                          54           0      0          100  0                                          55           20     10         100  0                                          57           0      0          100  0                                          68           0      0          100  20                                         73           0      0          100  0                                          74           0      0          100  0                                          76           0      0          100  0                                          77           0      0          100  0                                          78           0      0          100  70                                         83           0      0          100  0                                          85           0      0          100  100                                        86           0      0          100  73                                         ______________________________________                                    

As shown in Table 3, the compounds of the present invention of formula (I) have good insecticidal activity against diamond back moth (DBM) and miticidal activity against two-spotted spider mite (TSSM).

The compounds of formula (I) of present invention have good pre- and post-emergent herbicidal activity against upland and paddy weeds.

The herbicidal activity test was conducted according to the following methods.

(1) Screening for herbicidal activity in upland condition.

The sterilized sandy loam soil was mixed with a combined fertilizer and filled in test pots having a surface area of 348 cm². After seeding, the pots were covered with the soil finely sieved and kept in a greenhouse at 25° C. mean temperature.

Fourteen mg of each compound weighed for 4 kg/ha and was dissolved in 7 ml of acetone containing surfactant Tween-20, and diluted with the same amount of water. The solution on soil or foliage applied was in a spray volume of 14 ml/348 cm².

Test compounds were applied at 1 and 8-12 days after seeding for pre-emergence and post-emergence, respectively.

The pots were kept in the greenhouse for 2 or 3 weeks, and the herbicidal activity was visually observed on the basis of morphological and physicological symptoms by percent scale, in which 0 represents no activity and 100 represents complete control.

(2) Screening for herbicidal activity in flooded paddy condition.

A sandy loam soil mixed with a combined fertilizer and puddled with water to stick mud was filled in test pots having a surface area of 140 cm².

Two plant of rice seeding at 3rd leaf stage and sprouted rice seeds were transplanted and seeded, respectively. The pots are watered 3 cm deep just after planting. For 4 kg/ha application, 5.6 mg of each compound was dissolved in 2 ml of acetone containing 0.2% Tween-20 and diluted with the same amount of water. Four ml of the solution was applied on the water surface of the pot.

The pots were kept in the greenhouse for 2 or 3 weeks at 25° C. mean temperature, and the herbicidal activity was visually observed on the basis of morphological and physicologicaI symptoms by percent scale.

The plant species employed in these tests were selected from the followings:

Test plants for herbicide screening

    ______________________________________                                         Common Name Abbreviated Name                                                                            Scientific Name                                       ______________________________________                                         Upland                                                                         Corn        ZEAMX        Zea mays                                              Soybean     GLXMX        Glycine max                                           Cotton      GOSHI        Gossypium hispitum                                    Wheat       TRZAW        Triticum aestivum                                     Rice        ORYSA        Oryza sativa                                          Common sorghum                                                                             SORBI        Sorgum bicolor                                        Barnyardgrass                                                                              ECHOR        Echinochlor crus-galli                                Wheatgrass  AGRSM        Agropyron smithii                                     Large crabgrass                                                                            DIGSA        Digitaria sanguinalis                                 Fall panicum                                                                               PANDI        Pandicum dichotomiflorum                              Bindweed    CAGHE        Calystegia japonica                                   Cocklebur   XANSI        Xanthium strumarium                                   Velvetleaf  ABUTH        Abutilon avicennae                                    Indian jointvetch                                                                          AESIN        Aeschynomene indica                                   Black nightshade                                                                           SOLNI        Solanum nigrum                                        Green foxtail                                                                              STEVI        Setaria viridis                                       Orchard grass                                                                              DACGL        Dactylis glomerta                                     Japanese brome                                                                             BROJA        Bromus japonicus                                      Paddy                                                                          Rice        ORYSA        Oryza sativa                                          Barnyardgrass                                                                              ECHOR        Echinochlor crus-galli                                Bulrush     SCPJU        Scirpus juncoides                                     Monochoria  MOOVA        Monochoria vaginalis                                  Dayflower   ANEKE        Aneilema                                              Umbrellaplant                                                                              CYPDI        Cyperus diffomis                                      Falsepimpemel                                                                              LIDPY        Lindernia pyxidaria                                   Toothcup    ROTIN        Rotala indica                                         Flat-sedge  CYPSE        Cyperus serofinus                                     Arrow head  SAGPY        Sagittaria pygmaea                                    Water chestnut                                                                             ELOKU        Elocharis kuroguwai                                   Pondweed    PTMDI        Potamogeton distinctus                                Arrow head  SAGTR        Sagittaria trifolia                                   ______________________________________                                    

Herbicidal activity data of the present test chemical of formula (I) against upland and paddy weeds are shown in Table 4.

                                      TABLE 4                                      __________________________________________________________________________     Post-emergent herbicidal activity of the 4-amino-2-quinolinone                 derivatives (1)                                                                (rate = 4 kg/ha).                                                              Compound                                                                       No.   SORBI                                                                              ECHOR                                                                              AGRSM                                                                               DIGSA                                                                              PANDI                                                                              SOLNI                                                                              AESIN                                                                              ABUTH                                                                               XANSI                                                                              CAGHE                              __________________________________________________________________________     2     0   0   0    0   0   70  100 0    0   0                                  5     0   0   0    0   0   100 100 0    30  0                                  8     0   0   0    0   0   100 40  0    30  0                                  __________________________________________________________________________

                                      TABLE 5                                      __________________________________________________________________________     Herbicidal activity of 4-amino-2-quinolinone derivatives (1) to paddy          weeds.                                                                         Compound                                                                             ORYSA                                                                               ORYSA                                                               No.   (3-leaf)                                                                            (seed)                                                                             ECHOR                                                                               SCPJU                                                                              MOOVA CYPSE                                                                              SAGPY                                        __________________________________________________________________________     1     0    30  40   0   0     100 100                                          3     0    60  70   0   0     100 40                                           6     0    100 100  20  40    100 0                                            7     0    30  100  0   0     0   20                                           8     10   30  70   0   0     0   100                                          17    0    50  20   0   30    100 40                                           18    0    20  30   0   40    100 0                                            19    0    40  50   0   40    100 20                                           20    0    70  60   0   50    100 100                                          21    0    30  100  0   0     100 0                                            22    0    100 100  30  100   100 0                                            23    0    0   40   0   100   0   0                                            24    0    100 50   0   40    100 0                                            25    10   0   0    0   100   0   0                                            26    0    40  0    0   100   0   50                                           28    0    100 100  0   0     100 50                                           30    5    10  90   30  60    100 0                                            35    30   100 100  50  80    100 0                                            38    10   100 100  30  100   100 100                                          43    10   10  0    100 10    40  0                                            44    0    10  100  50  100   20  0                                            46    10   100 70   20  60    100 30                                           54    0    100 100  100 100   100 0                                            57    0    20  100  30  0     100 100                                          67    10   100 100  30  100   100 0                                            68    10   100 100  0   100   100 0                                            74    10   10  100  0   10    0   0                                            85    0    10  100  0   0     0   20                                           92    5    10  100  10  30    40  10                                           102   0    20  100  0   60    0   0                                            __________________________________________________________________________

Useful formulations of the compounds of formula (I) can be prepared by mixing the the active ingredients about 0.01˜90 by weight % with proper solid or liquid carrier and supporters such as surfactant, diluent, spreader, synergist, adhesive, and dispersant, etc.

The used solid carrier may be chosen from the inorganic powders such as attapulgite clays, the montmorillonite days, the diatomaceous earths, kaolinite, bentonite, mica, gypsum, calcium carbonate, apitite, synthesized silicone hydroxide hydrate or plant powders.

And as liquid carriers, alcohols such as methanol, ethanol, ethylene glycol; aromatic hydrocarbons such as benzene, xylene, toluene, naphtha; halohydrocarbons such as chloroform, carbon tetrachloride; ethers such as tetrahydrofurane, dioxane; ketones such as acetone, methyl ethyl ketone; esters such as ethyl acetate, butyl acetate, ethylene glycole acetate; amides such as dimethylformamide; nitriles such as acetonitrile; ether alcoholes such as ethylene glycol diethyl ether, or water etc. can be used.

Surfactants can be various cationic, anionic and nontoxic surfactants.

Cationic surfactants include long chain alkylammoniun salts such as cetyltrimethylammonium bromide, etc.

Anionic surfactants include alkali metal, alkaline earth metal and ammonium salts of alkylaryl sulfonic acids such as dodecyl benzenesulfonic acids; alkylsulfonic acids such as laurylsulfonic acids ligninsulfonic acid; arylsulfonic such as naphthylenesulfonic acid; lauryl ether sulfate; fatty alcohol sulfates; fatty acids; salt of sulfated hexadecanols, octadecanols; salts of sulfated fatty alcohol glycol ethers, etc.

Examples of nonionic surfactants include condensation products of fatty alcohols such as oleyl alcohol or cetyl alcohol; phenols; alkylphenols or caster oil with ethylene oxide or propylene oxide; polyoxy ethylene alkylphenylether; poly oxyethylene fatty acid ester, etc.

Polyvinylalcohol, CMC, gum arabic, etc. can be used as adhesive.

The compositions of the compounds of the present invention may be manufactured as formulation such as powder, wettable powder, granules, emulsifiable concentrates, suspensions, solution, fumigant, gas phase, etc., and their formulations can be used on earth, agricultural products, seedling, seeds, etc.

For example, emulsifiable concentrates or solution may be prepared by uniformly dissolving the compound of formula (I) with hydrocarbon, acetone or alcohol and surfactant.

Wettable powders, which may be compacted to form water dispersible granules, may comprise an intimate mixture of the active compound, inert carrier and surfactants.

The combinations including the compounds according to the present invention may be used by mixing with agricultural chemicals such as insecticides, fungicides, herbicides, plant growth regulants, fertilizer, miticides, or other agricultural chemicals.

Especially, since the known fungicides have resistance, the compounds of formula (I) of more than 1 weight % may be used with the known fungicides including following compounds;

1) N-substituted azoles, for example, prochloraz, triademefon, and flusitazol;

2) pyrimidines, such as fenarimol and nuarimol;

3) morpholines, such as fenpropimorph and tridemorph;

4) piperazines, such as triforine;

5) pyridines, such as pyrifenox;

6) dithiocarbamates, such as maneb and mancozeb;

7) phthalimides, such as captafol;

8) isophthalonitriles, such as chlorothalonil;

9) dicarboximides, such as ipmdione;

10) benzimidazoles, such as benomyl and carbendazim;

11) 2-aminopyrimidines, such as ethirimol;

12) carboxamides, such as carboxin; and

13) dinitrophenols, such as dinocap.

The fungicide combinations of the invention contain at least 1%, generally 20˜80% by weight of a compound of formula (I). 

What is claimed is:
 1. A compound of 4-amino-2-quinolinone derivatives of the formula (I): ##STR152## wherein, R₁, R₂, R₃ and R₄ are independently hydrogen, halogen, C₁ -C₁₀ alkyl, C₁ -C₃ haloalkyl, C₁ -C₈ alkoxy, C₁ -C₃ haloalkoxy, C₁ -C₃ alkylthio, C₁ -C₃ haloalkylthio, NO₂, CN, C₁ -C₄ alkoxy carbonyl, phenyl, phenoxy, benzoyl, benzenesulfonyl, benzyl or morpholine;R₅ is hydrogen, C₁ -C₆ alkyl, cyclopropyl, phenyl, halophenyl, benzyl or phenylthiomethyl; R₆ is hydrogen, C₁ -C₅ alkyl, C₃ -C₆ alkenyl or C₃ -C₆ alkynyl; R₇ is ##STR153## wherein, R₈, R₉ and R₁₀ are independently hydrogen, halogen, phenyl or alkynyl, wherein R₈, R₉ and R₁₀ are not hydrogen at same time; R₁₁, R₁₂, R₁₃, R₁₄, R₁₅ and R₁₆ are independently hydrogen, halogen, C₁ -C₆ alkyl, alkoxyalkyl, halophenyl, phenyl or (R₂₀)₃ Si; R₁₇ is hydrogen or C₁ -C₅ alkyl; R₁₈ and R₁₉ are C₁ -C₅ alkyl; X is oxygen or sulfur; Y is sulfur or --S(═O)--; R₂₀ is C₁ -C₅ alkyl; m, n, p and q are 0 to 4; andwherein if R₁₇ is hydrogen and n is 0, 1 or 2 then R₁₈ is C₃ -C₅ alkyl.
 2. The compound of 4-amino-2-quinolinone derivatives or the formula (I) according to claim 1 wherein,R₁, R₂, R₃ and R₄ are independently hydrogen, halogen, C₁ -C₆ alkyl, CF₃, NO₂, CN; R₅ is C₁ -C₄ alkyl, cyclopropyl, halophenyl, benzyl; R₆ is hydrogen, C₁ -C₅ alkyl, C₃ -C₆ alkenyl or C₃ -C₆ alkynyl; R₇ is ##STR154## wherein: R₈, R₉ and R₁₀ are hydrogen, halogen, phenyl or alkynyl, wherein R₈, R₉ and R₁₀ are not hydrogen at same time; R₁₁, R₁₂, R₁₃, R₁₄, R₁₅ and R₁₆ are hydrogen, halogen, C₁ -C₆ alkyl, alkoxyalkyl, phenyl or (R₂₀)₃ Si; R₁₇ is hydrogen or C₁ -C₅ alkyl; R₁₆ and R₁₉ are C₁ -C₅ alkyl; X is oxygen or sulfur; Y is sulfur or --S(═O)--; R₂₀ is C₁ -C₅ alkyl; m, n, p and q are 0 to 4; andwherein if R₁₇ is hydrogen and n is 0, 1 or 2 then R₁₈ is C₃ -C₅ alkyl.
 3. A fungicidal composition comprising a fungicidally effective amount of 4-amino-2-quinolinone derivatives of formula (I) as claimed in claim
 1. 4. An insecticidal composition comprising a insecticidally effective amount of 4-amino-2-quinolinone derivatives of formula (I) as claimed in claim
 1. 5. A herbicidal composition comprising a herbicidally effective amount of 4-amino-2-quinolinone derivatives of formula (I) as claimed in claim
 1. 